CN114506879A - Integrated method for preparing cobalt-free lithium-rich cathode material and regulating and controlling oxygen activity of crystal lattice of cobalt-free lithium-rich cathode material - Google Patents
Integrated method for preparing cobalt-free lithium-rich cathode material and regulating and controlling oxygen activity of crystal lattice of cobalt-free lithium-rich cathode material Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 144
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000010406 cathode material Substances 0.000 title claims abstract description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- 239000001301 oxygen Substances 0.000 title claims abstract description 29
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 29
- 230000000694 effects Effects 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000013078 crystal Substances 0.000 title claims abstract description 19
- 230000001276 controlling effect Effects 0.000 title claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 8
- 239000011029 spinel Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000007599 discharging Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 230000001351 cycling effect Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 230000033228 biological regulation Effects 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
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- 239000004005 microsphere Substances 0.000 description 2
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- 239000002244 precipitate Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- -1 transition metal cations Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a preparation method of a cobalt-free lithium-rich anode material and an integrated method for regulating and controlling the oxygen activity of crystal lattices of the cobalt-free lithium-rich anode material, which comprises the following steps of: pre-sintering a cobalt-free lithium-rich precursor into a cobalt-free lithium-rich precursor oxide; and uniformly mixing the cobalt-free lithium-rich anode precursor oxide with a lithium source, carrying out high-temperature heat treatment, and cooling along with the furnace to obtain the cobalt-free lithium-rich anode material. According to the invention, the internal structure of the crystal of the cobalt-free lithium-rich cathode material is regulated and controlled by regulating and controlling the content proportion of the lithium source, and the electrochemical specific capacity, the structural stability and the cycle performance of the cobalt-free lithium-rich cathode material are improved; by regulating and controlling the content of the lithium source, different degrees of cation mixed-discharging and spinel or rock salt phases are generated in the cobalt-free lithium-rich cathode material, the activity of lattice oxygen in the cobalt-free lithium-rich cathode material is regulated and controlled, and the comprehensive electrochemical performance of the lithium-rich cathode material is improved. The method is simple to operate, effectively simplifies the secondary processing of the post-treatment on the material, reduces the production cost, and is suitable for industrial mass production.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an integrated method for preparing a cobalt-free lithium-rich cathode material and regulating and controlling the oxygen activity of crystal lattices of the cobalt-free lithium-rich cathode material.
Background
The lithium ion battery has the advantages of high specific energy, high energy storage efficiency, long service life and the like, and is widely applied to the fields of 3C electronic products, electric automobiles, power grid energy storage and the like; however, the conventional lithium ion battery is difficult to meet the requirements of the future market for higher energy density and lower cost, and needs to be upgraded urgently. In the lithium ion battery, the cathode material is mainly a carbon-based material, the anode material is continuously developed, and the anode material plays a decisive role in the energy density and the cost of the lithium ion battery and is the most key material for promoting the upgrading and optimization of the lithium ion battery industry. The development requirement of the industry on the lithium ion battery determines the technical indexes of the cathode material, wherein the most important is the specific energy, the cycle performance and the cost, the higher the specific energy is, more kinetic energy can be provided, and the material cost of the unit energy density (Wh/kg) is also reduced; the longer the cycle life, the lower the practical use cost of the battery. Therefore, performance improvement and cost reduction are necessary requirements for developing the positive electrode material of the lithium ion battery.
Meanwhile, the cobalt-free lithium-rich cathode material has the advantages of high specific capacity, high working voltage and the like, can well meet the development requirements of low cost and high performance, and is a next-generation cathode material with great potential for lithium ion batteries. However, the cobalt-free lithium-rich layer cathode material has the problem that the activity of lattice oxygen is difficult to regulate, insufficient activation of lattice oxygen can cause that capacity cannot be exerted, but too sufficient activation can cause excessive extraction of lattice oxygen, transition metal migration is promoted, the material is subjected to layered-spinel phase transformation, and the capacity voltage, the cycle performance and the rate performance of the material are attenuated accordingly. Therefore, the method for exploring the method capable of effectively regulating and controlling the lattice oxygen activity of the cobalt-free lithium-rich cathode material and simultaneously improving the electrochemical performance of the cobalt-free lithium-rich cathode material has important scientific significance and wide application prospect.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an integrated method for preparing a cobalt-free lithium-rich cathode material and regulating and controlling the oxygen activity of crystal lattices thereof, wherein the internal structure of the crystal of the cobalt-free lithium-rich cathode material is regulated and controlled by regulating and controlling the content proportion of a lithium source, so that the electrochemical capacity, the structural stability and the cycle performance of the cobalt-free lithium-rich cathode material are improved; by regulating and controlling the content of the lithium source, different degrees of cation mixed-discharging and rock salt phases are generated in the cobalt-free lithium-rich anode material, the activity of lattice oxygen in the cobalt-free lithium-rich anode material is regulated and controlled, and the comprehensive electrochemical performance of the lithium-rich anode material is improved.
In order to achieve the above purpose, one of the technical solutions of the present invention is: an integrated method for preparing a cobalt-free lithium-rich cathode material and regulating and controlling the oxygen activity of crystal lattices of the cobalt-free lithium-rich cathode material specifically comprises the following steps:
(1) pre-sintering a cobalt-free lithium-rich precursor into a cobalt-free lithium-rich precursor oxide;
(2) and uniformly mixing the cobalt-free lithium-rich anode precursor oxide with a lithium source, carrying out high-temperature heat treatment, and cooling along with a furnace to obtain the cobalt-free lithium-rich anode material.
In a preferred embodiment of the present invention, the pre-sintering in step (1) has a temperature rise rate of 1-15 ℃/min, and is calcined in air at 400-600 ℃ for 1-5h, and then is cooled with the furnace.
In a preferred embodiment of the present invention, the cobalt-free lithium-rich precursor in step (1) is at least one of hydroxide, carbonate and oxalate precipitates.
In a preferred embodiment of the present invention, the lithium source in the step (2) is at least one of lithium hydroxide, lithium carbonate and lithium chloride.
In a preferred embodiment of the present invention, the mass ratio of the lithium source in the step (2) is 70% to 90% of the mass ratio of the cobalt-free lithium-rich precursor oxide.
Further, the mass ratio of the lithium source in the step (2) is 73-81% of the mass ratio of the cobalt-free lithium-rich precursor oxide.
In a preferred embodiment of the present invention, the temperature of the heat treatment in step (2) is 700-950 ℃, the time is 8-15h, and the heat treatment atmosphere is air or oxygen.
In order to achieve the above purpose, the second technical solution of the present invention is a cobalt-free lithium-rich cathode material prepared by an integrated method of preparing a cobalt-free lithium-rich cathode material and regulating the oxygen activity of crystal lattice thereof, wherein the chemical formula of the cobalt-free lithium-rich cathode material is Li1+a[MnxNiyMz]1-aO2Wherein a is more than or equal to 0 and less than or equal to 0.3, x + y + z is 1, x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.065, and M is at least one element of metals such as Na, K, Fe, Al, W, Nb, Ti, Zr, V and the like; when a is less than 0.2, the formation of larger cation mixed rows and spinel or rock-salt phase structures is initiated.
In a preferred embodiment of the invention, the molar ratio of Mn to Ni in the cobalt-free lithium-rich cathode material is from 2.5 to 4: 1.
Furthermore, the molar ratio of Mn to Ni in the cobalt-free lithium-rich cathode material is 3-3.4: 1.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the structure of the finally synthesized cobalt-free lithium-rich anode material is regulated and controlled by changing the mass content proportion of the lithium source in the cobalt-free lithium-rich precursor oxide in the lithium mixing and calcining process, cation mixed discharge is induced in the lithium-rich material, rock salt phases with different degrees can be generated in the cobalt-free lithium-rich anode material and on the surface of the cobalt-free lithium-rich anode material according to the difference of the lithium source content, the diffusion rate of lithium ions and the electrochemical activity of lattice oxygen can be regulated and controlled by the cation mixed discharge and spinel or rock salt phases with different degrees, the high electrochemical capacity of the cobalt-free lithium-rich anode material is finally realized, and the structural stability and the cycle performance of the cobalt-free lithium-rich anode material are improved.
2. According to the invention, the content of the lithium source is regulated and controlled to induce different degrees of cation mixed-discharging and spinel or rock salt phases to be generated in the cobalt-free lithium-rich cathode material, so that the activity of lattice oxygen in the cobalt-free lithium-rich cathode material is effectively regulated and controlled, and the comprehensive electrochemical performance of the lithium-rich cathode material is improved; the method can realize the synchronous regulation and control of the lattice oxygen and the electrochemical performance in the sintering preparation process of the lithium-rich anode material, has simple operation, effectively simplifies the secondary processing of the material by post-treatment and reduces the production cost.
3. In addition, in the process of high-temperature thermal treatment after the cobalt-free lithium-rich anode precursor oxide and a lithium source are uniformly mixed, the diffusion of transition metal cations and lithium ions can occur, the rapid temperature rise breaks the balance of the diffusion to a certain extent, and the cation mixed-discharging degree can be increased, so that the internal structure of the crystal is changed, and the lattice oxygen activity in the cobalt-free lithium-rich anode material is regulated and controlled.
4. The invention is simple, integrates preparation and modification, does not need post-treatment process and is suitable for industrial mass production.
Drawings
Fig. 1 is an X-ray diffraction pattern of cobalt-free lithium-rich cathode sample 1 in example 1 of the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) morphology of the cobalt-free lithium-rich cathode sample 1 in example 1 of the present invention.
FIG. 3 is a Transmission Electron Microscope (TEM) high resolution image of the cobalt-free lithium-rich cathode sample 1 in example 1 of the present invention.
Fig. 4 shows the cycling performance of the button cell of cobalt-free lithium-rich positive electrode sample 1 of example 1 of the present invention.
Fig. 5 is an X-ray diffraction pattern of cobalt-free lithium-rich cathode sample 2 in example 2 of the present invention.
Fig. 6 is a Scanning Electron Microscope (SEM) morphology of the cobalt-free lithium-rich cathode sample 2 in example 2 of the present invention.
FIG. 7 is a Transmission Electron Microscope (TEM) high resolution image of the cobalt-free lithium-rich cathode sample 2 in example 2 of the present invention.
Fig. 8 is a graph of cycling performance of button cells of cobalt-free lithium-rich positive electrode sample 2 of example 2 of the invention.
Detailed Description
An integrated method for preparing a cobalt-free lithium-rich cathode material and regulating and controlling the oxygen activity of crystal lattices of the cobalt-free lithium-rich cathode material specifically comprises the following steps:
(1) pre-sintering a cobalt-free lithium-rich precursor into a cobalt-free lithium-rich precursor oxide;
(2) and uniformly mixing the cobalt-free lithium-rich anode precursor oxide with a lithium source, carrying out high-temperature heat treatment, and cooling along with a furnace to obtain the cobalt-free lithium-rich anode material.
The temperature rising rate of the pre-sintering in the step (1) is 1-15 ℃/min, the calcination is carried out for 1-5h in the air at the temperature of 400-600 ℃, and then the calcination is carried out along with the furnace cooling.
The cobalt-free lithium-rich precursor in the step (1) is at least one of hydroxide, carbonate and oxalate precipitates.
And (3) in the step (2), the lithium source is at least one of lithium hydroxide, lithium carbonate and lithium chloride.
In the step (2), the mass ratio of the lithium source is 70-90% of the mass of the cobalt-free lithium-rich precursor oxide.
In the step (2), the mass ratio of the lithium source is 73-81% of the mass of the cobalt-free lithium-rich precursor oxide.
The temperature of the heat treatment in the step (2) is 700-950 ℃, the time is 8-15h, and the heat treatment atmosphere is air or oxygen.
Preparation of cobalt-free lithium-rich cathode material and cobalt-free lithium-rich cathode material prepared by integrated method of crystal lattice oxygen activity regulation and control of cobalt-free lithium-rich cathode material, wherein the chemical formula of the cobalt-free lithium-rich cathode material is Li1+a[MnxNiyMz]1-aO2Wherein a is more than or equal to 0 and less than or equal to 0.3, x + y + z is 1, x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.065, and M is at least one element of metals such as Na, K, Fe, Al, W, Nb, Ti, Zr, V and the like; when a is less than 0.2, the formation of larger cation mixed rows and spinel or rock-salt phase structures is initiated.
The molar ratio of Mn to Ni in the cobalt-free lithium-rich cathode material is 2.5-4: 1.
The molar ratio of Mn to Ni in the cobalt-free lithium-rich cathode material is 3-3.4: 1.
The invention is further explained below with reference to the figures and the specific embodiments.
The cobalt-free lithium-rich cathode precursor oxides in the following examples are all Mn0.62Ni0.18O2The preparation method comprises the following steps: 5g of cobalt-free lithium-rich positive electrode precursor Ni0.18Mn0.62CO3Placing in a muffle furnace, heating at a rate of 10 ℃/min, calcining at 500 ℃ in air for 2h, and cooling with the furnace to obtain a precursor oxide Mn0.62Ni0.18O2。
Example 1
Uniformly mixing 1g of the cobalt-free lithium-rich anode precursor oxide with 0.78g of lithium hydroxide, heating to 800 ℃ at a heating rate of 10 ℃/min in the air, preserving the temperature for 10 hours, and cooling along with the furnace to obtain a cobalt-free lithium-rich anode sample 1, wherein the chemical formula of the cobalt-free lithium-rich anode material is Li1.1836Mn0.6174Ni0.1826O2(obtained from inductively coupled plasma mass spectrometry ICP test data).
XRD observation is carried out on the cobalt-free lithium-rich cathode sample 1, an XRD characteristic diffraction peak spectrum shown in figure 1 is obtained, and as can be seen from the figure, a main peak corresponds to a lamellar phase (R-3m) and a lithium-rich phase (C2/m), the main peak has a typical structure of a lithium-rich material, and a diffraction peak with a weaker degree of 20-25 completely corresponds to Li2MnO3Lithium rich phase (C2/m).
The appearance of the cobalt-free lithium-rich cathode sample 1 is observed by SEM, and the SEM appearance image shown in fig. 2 is obtained, from which it can be seen that the cobalt-free lithium-rich cathode sample 1 is a microsphere assembled by nanoparticles and has a diameter of about 12 μm.
TEM observation of the cobalt-free lithium-rich cathode sample 1 gave a TEM high resolution as shown in fig. 3, which revealed that the cobalt-free lithium-rich cathode sample 1 had a good layered structure and good crystallinity.
Firstly, mixing a cobalt-free lithium-rich positive electrode sample 1, conductive carbon and a binder to prepare uniform slurry, then coating the slurry on an aluminum foil for drying, rolling and cutting, finally assembling a button cell by matching a diaphragm and a lithium metal sheet, and testing the specific discharge capacity. The result is shown in fig. 4, and it can be seen from the cycling curve on the graph that the button cell of the cobalt-free lithium-rich cathode sample 1 has a specific discharge capacity of 225.2mAh/g when cycled in a voltage range of 2-4.8V and a current density of 250mA/g, and has a capacity retention rate of 94.8% after 200 cycles of cycling, and shows a high specific discharge capacity and excellent cycling stability.
Example 2
Using the same preparation method as in example 1 except for using 0.73g of lithium hydroxide as lithium hydroxide, a cobalt-free lithium-rich positive electrode sample 2 was obtained, the chemical formula of sample 2 being Li1.1156Mn0.6161Ni0.1839O2。
Fig. 5 shows the XRD characteristic diffraction peak spectrum of the cobalt-free lithium-rich cathode sample 2, and a certain amount of a rock salt phase peak appears.
As shown in the SEM image of fig. 6, the cobalt-free lithium-rich cathode sample 2 is a microsphere assembled from nanoparticles.
As shown in the TEM high resolution image of fig. 7, a distinct rock salt phase or spinel phase appears on the surface of sample 2.
A button cell containing cobalt-free lithium-rich positive electrode sample 2 was obtained in the same manner as in example 1, and as shown in the cycling curve of fig. 8, the button cell had a specific discharge capacity of 96.0mAh/g when cycled over a voltage range of 2-4.8V and a current density of 250mA/g, and a specific discharge capacity of 222.0mAh/g after 200 cycles.
Example 3
Using the same preparation method as in example 1 except for using 0.75g of lithium hydroxide as lithium hydroxide, a cobalt-free lithium-rich positive electrode sample 3 was obtained, the chemical formula of sample 3 being Li1.1430Mn0.6163Ni0.1837O2。
A button cell containing a cobalt-free lithium-rich positive electrode sample 3 was obtained in the same manner as in example 1, and had a specific discharge capacity of 147.6mAh/g when cycled over a voltage range of 2-4.8V and a current density of 250mA/g, and a specific discharge capacity of 221.4mAh/g after 200 cycles.
Example 4
Using the same preparation method as in example 1 except that 0.81g of lithium hydroxide was used, a cobalt-free lithium-rich cathode sample 4 was obtained, the chemical formula of sample 4 being Li1.2212Mn0.6343Ni0.1891O2。
A button cell containing a cobalt-free lithium-rich positive electrode sample 4 was obtained in the same manner as in example 1, and had a specific discharge capacity of 211.4mAh/g when cycled over a voltage range of 2-4.8V and a current density of 250mA/g, and a specific discharge capacity of 189.5mAh/g after 200 cycles.
The above embodiments are merely preferred embodiments of the present invention, which are provided for illustrating the principles and effects of the present invention and not for limiting the present invention. It should be noted that modifications to the above-described embodiments can be made by persons skilled in the art without departing from the spirit and scope of the present invention and such modifications should also be considered as within the scope of the present invention.
Claims (10)
1. An integrated method for preparing a cobalt-free lithium-rich cathode material and regulating and controlling the oxygen activity of crystal lattices thereof is characterized by comprising the following steps of:
(1) pre-sintering a cobalt-free lithium-rich precursor into a cobalt-free lithium-rich precursor oxide;
(2) and uniformly mixing the cobalt-free lithium-rich precursor oxide with a lithium source, carrying out high-temperature heat treatment, and cooling along with the furnace to obtain the cobalt-free lithium-rich cathode material.
2. The integrated method for preparing the cobalt-free lithium-rich cathode material and regulating and controlling the oxygen activity of the crystal lattice thereof as claimed in claim 1, wherein the pre-sintering in the step (1) has a temperature rise rate of 1-15 ℃/min, is calcined in the air at 400-600 ℃ for 1-5h, and is then cooled with a furnace.
3. The integrated method for preparing the cobalt-free lithium-rich cathode material and regulating the oxygen activity of the crystal lattice thereof according to claim 1, wherein the cobalt-free lithium-rich precursor in the step (1) is at least one of hydroxide, carbonate and oxalate precipitation.
4. The integrated method for preparing the cobalt-free lithium-rich cathode material and regulating the oxygen activity of the crystal lattice thereof as claimed in claim 1, wherein the lithium source in the step (2) is at least one of lithium hydroxide, lithium carbonate and lithium chloride.
5. The integrated method for preparing the cobalt-free lithium-rich cathode material and regulating the oxygen activity of the crystal lattice thereof according to claim 1, wherein the mass ratio of the lithium source in the step (2) is 70-90% of the mass ratio of the cobalt-free lithium-rich precursor oxide.
6. The integrated method for preparing the cobalt-free lithium-rich cathode material and regulating the oxygen activity of the crystal lattice of the cobalt-free lithium-rich cathode material as claimed in claim 1, wherein the mass ratio of the lithium source in the step (2) is 73% -81% of the mass ratio of the cobalt-free lithium-rich precursor oxide.
7. The integrated method for preparing the cobalt-free lithium-rich cathode material and regulating the oxygen activity of the crystal lattice thereof as claimed in claim 1, wherein the temperature of the heat treatment in the step (2) is 700-950 ℃, the time is 8-15h, and the heat treatment atmosphere is air or oxygen.
8. A cobalt-free lithium-rich positive electrode material prepared according to the method of any one of claims 1 to 7, wherein the cobalt-free lithium-rich positive electrode material has a chemical formula of Li1+a[MnxNiyMz]1-aO2Wherein a is more than or equal to 0 and less than or equal to 0.3, x + y + z is 1, x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.065, and M is at least one of Na, K, Fe, Al, W, Nb, Ti, Zr and V metals; when a is less than 0.2, the formation of larger cation mixed rows and surface spinel or rock salt phase structure is initiated.
9. The cobalt-free lithium-rich cathode material as claimed in claim 8, wherein the molar ratio of Mn to Ni in the cobalt-free lithium-rich cathode material is 2.5-4: 1.
10. The cobalt-free lithium-rich cathode material as claimed in claim 8, wherein the molar ratio of Mn to Ni in the cobalt-free lithium-rich cathode material is 3-3.4: 1.
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| CN113636606A (en) * | 2021-07-13 | 2021-11-12 | 北京科技大学 | Preparation method and application of nickel-rich cobalt-free single crystal cathode material of lithium ion battery |
| CN113690414A (en) * | 2021-07-29 | 2021-11-23 | 北京理工大学重庆创新中心 | Mixed lithium-rich cathode material and preparation method and application thereof |
| US20210384506A1 (en) * | 2020-06-05 | 2021-12-09 | The Regents Of The University Of California | Electrode including a layered/rocksalt intergrown structure |
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| US20210184212A1 (en) * | 2017-11-20 | 2021-06-17 | Ningbo Institute Of Materials Technology And Engineering, Chinese Academy Of Sciences | Lithium-rich oxide positive electrode material, preparation method therefor, and lithium ion battery |
| US20210384506A1 (en) * | 2020-06-05 | 2021-12-09 | The Regents Of The University Of California | Electrode including a layered/rocksalt intergrown structure |
| CN113636606A (en) * | 2021-07-13 | 2021-11-12 | 北京科技大学 | Preparation method and application of nickel-rich cobalt-free single crystal cathode material of lithium ion battery |
| CN113690414A (en) * | 2021-07-29 | 2021-11-23 | 北京理工大学重庆创新中心 | Mixed lithium-rich cathode material and preparation method and application thereof |
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| CN116655004A (en) * | 2023-07-03 | 2023-08-29 | 湖南镓睿科技有限公司 | Cobalt-free positive electrode material and preparation method and application thereof |
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